Amino-anthraquinone derivatives and process of making same



I if Patented poet;

M osqnrt BAR Ann renneitossivrnnmor BASEL, SWITZERLAND, ASSIGNORS TOsocrn'rz or cnnmcen'rnnnsray m BASLE, or BASEL, SWITZERLANDAmmo-nivrirrmoumonn DERIVATIVES 'AN'D rnocnss on MAKING .smn

Drawing. Application flled J'uly 16, 192$,Seria1LNd. 293,302, and inswlt'z e i'land August 4, 1927. a

This invention relates to the manufacture 'oflnewproducts bycausing analdehyde 'which contains more than one carbon atom to act, in the formof itsbisulfite compound, corin presence of bisulfite, on ananthraquinlone derivative which contains at leastc one amino groupcontaining itself at least one hydrogen atom. Suchanthraquinone deriva-Znumbers in literature; The new products can'be obtained 1n sol d tivesare described or fmentioned in large 7 v form-by salting out orcautiouslyevaporating their solutions, or,otherwiseg They form orange,red, vil;et,';'blue or darkpowders which dissolve in water by formingorange H or red or violet or blue to greenish-blue s0-,

.7; 'lutions. They are suitable for many purposes for instance forprinting cotton and silk and particularlyfor dyeing acetyl-cel w'lulose. The advantage of using them resides in the factthat they arevery easily dissolved or ;disperse'din water and that from theirsolutions or suspensions vthey are dyeing acetyl-celluloseoracetate silkin a smooth quinone of the formula y E manner. a I j The followingexamples illustrate the inventiemthe arts being;,hy;weight '7 Example 1a c parts; of, 4,: 5 et r arei heatedfwhilestirring, with parts f volumeof commercial sodium bisulfite liquor and. -,Parts of water for 1 hourat 90 C.

until I all has passed into solution. This solution may be used directlyfor dyeing or may be evaporated to dryness, in which case a powdercompletely soluble in water is obtained. Acetate silk may be dyed withthis product as follows: 1 part of this dyestuff is dissolved orsuspended in 300 parts of PATENT waterand ijOparts of acetate silk areintro duced into the'solution at LO-50 C. The

bathis heated'to 75 C. and maintained at Y this temperature for 4 hour.The material is then washed, dried and, .if necessary,

brightened. The acetate silk is dyed in fast bright 'blue tints. In likemanner furfurol may be used for obtaining a product which apparentlycorresponds with an w-furfurylsulfonic acid. Like products are obtainedwhenfcroton aldehyde or acetaldehyde is used. P l l a 4 a The examplemay be carried out with "otheraminoanthraquinones than that named,

for instance 1:4-,;1:5 -"0r lz8-diaminoan- Y thraquinone; the'variousl-alkylor l-aralkylor v 1 aryl amino 4 aminoanthraquinones, such as1-aminomethyl-t-aminoanthra- 'quinone, l-phenylarninoeat-aminoanthraquinone, 1-amino-4- (4 -amino.) -phenylaminoanthraquinone;polya'niinoarylamino an thraquinon'es'; such as 1:5-diamin0-4-phe-.nylaminoanthraquinones I or 1,: 5-diaminoi8-diphenylaminoanthraquinone; the hydroxy-derivatives, such as lzi-aminohy dro'xyor 1 5-diamino-t: 8-dihydroxyanthra'quinone;" thehalogenaminoanthraquinones, suchjas 5-ch1oro 1:4-amin0anthraqumone, 7 y1 EmampZeE the formula v 0 NH:

one 0 I parts" of 1eamino 4ehydroxyanthraquinare stirred with 180 partsof a mixture of. 500 parts of ammonium bisulfite of 40 per cent strengthand 200 partsof benzaldelhyde, until a clear solution is produced. I

Probably the following reaction has taken place: r c f I: a i

. .E l l grams 7 of 'monometliyl-Ltdiamino-am thraquinone are introduced"While stirring 1 well into asolution of 40 grams of benzaldehyde inammonium bisulfi'te ofAO percent. strength; to. this susp ension'lOdrops of concentrated, formic acid of 83.5 per cent.

strength are added. After a short'time it .dissolvesatiordinarytemperature whereby the rnass becomes intensively." blue colored. Afterstirring during 24 hours. partials-eparation of bronze glittering smallcrystals occurs at ordinary temperature. By "addition of com. ofwaterthe mass istrans formed to dry content of 10 per cent.) Thep'roductthus obtained is a bronzeglittering paste which dissolves inaterand particu larly in water containing somewhat of am,- moniatoviolet-blue coloration. i Byf filter'ing'with suction the abovedescribed dyestuiii paste, and by pressing off and drying there 'isobtained" a deep-blue powderwhich. dissolvesvery easily in water;

1; A manufacture -dr--'new 'anthraquinone derivatives by causing analdehydewhich containsmorethan one carbon atom to act in presence ofalkali (this ,expressionflincluding also ammonium) bisulfite onananfthraquinone derivative, which contains] at also, ammonium) bisulfiteon an anthraqu-inone derivativeavhich 1 contains at least one primaryammo-group.

silk, similar tints.

similar tints.

V 4. Amanufacture of new anthraquinone causing benzaldehyde to actderivatives b in presence oi alkali (this expression includ-' ing alsoammonium) bisu'lfite on an anthraquinone derivative which contains atleast two amino-groups of which at least one is a primary amino-group.

5. A manufactureof new anthraquinone derivatives by causingbenzaldehyde'to act in presence. of alkali (thisexpre'ssion includingalso-ammonium) bisulfite on ananthra-- quinon'e de'rivativewhichxcontains at least two Ia-ammo-groups of which at least 0118,15

a primary amino-group. .6. A manufacture ofnew .antl'ira'quinone inpresence of alkali v(thisexpressio pincludlngalso ammomum) blsulfite onan anthra jquinone derivative. which; ,co'ntain'sfi at; least fourwamino-groups of which at are primary amino-groups.

least two so "derivatives by causingtenzaldehyde to act Y 7. As newproductsthe compounds'which are obtained by'causing'an aldehyde which,

contains, more thanone carbon. atom to:act in presence of alkali(thisexpression including also ammonium) bisulfite on an anthraquin onederiyative which contains at leastone primary amino-group, whichproducts form orange,-red, blue or-dark powders, disperse i'n water'toorange, red, Violet or blue coloration and dye from aqueous dyeing-bathsesters 5 and ethers ofcellulose, particularly acetate n d t w compoundsthat are obtained by causing an aldehyde which contains: more than 6carbon atoms to act in presence'of alkali this expression including alsoammonium).bisullite on an anthraquin-L 'onefderi'vative' which containsatl'east one primaryv aminogroup, wh ch products form orange,'red,blue'or darkpowders, disperse in waterto orange, red, violet or bluecoloration and'dye from aqueous dyeing-baths esters and vtliers ofcellulose, arti ye silk 9. As new "products I the compounds which inpresence of alkali (this expression including also ammonium):bisulfiteon an anthra quin'one derivative which contains atleast one primaryammo-group, which products form orange, red,"blue or dark powders,disperse in water to orange, red, violet or blue coloration and dye fromaqueous dyeing-baths esters and 1120 ethers of cellulose,particularlyacetate silk, similartints, i i

10. As new c are obtainediby causing benzaldehyde to act produots the'compounds which l are obtained by causinghenzaldehyde to act i l Pr s tlkel h s lp iss oni c r dingal'so ammon um) blsuliite on} nanthjraduinonederivativewhich contains at least twoamino-groups': of whichatf'least one a prnnary amino-group, wh ch products form orange,red,"bl'ue. or dark powders,"disp'erse in water-t0 red, violetor'blue'coloration and dye i I from aqueous dyeil lg baths esters andethers :of cellulose, particularly acetate silk, similar tints. Y v11.As new products the compounds which ,5 are obtainedby causingbenzaldehyde to act in presence-of alkali (this expression includi a Iing also ammoniumybisulfite onan anthra- V quinone' derivative which;contains at least two a-ammo-groupsof whlch at least 011615 a I primaryamino-group, which products form" v-orange, red; blue or dark powders;disperse 1n water to red, violet or blue coloration'and dye from aqueousdyeing-baths esters and ethers of cellulose, particularly acetatesilk,similar '15 tints. Y

, 12. As new productstlie compoundswhich v i Y I are obtainedby causingbenzaldehyde to act lin presenceof alkalifthis expression includ-v ingalso ammoiiiumybisulfite on an anthrae 20 quinone derivatii e whichcontains at least vfour a-aminoegr0ups of which at least one isethersiofcellulose,.particularly acetate silk,

"similar tints. H

13. Material dyedf with'the (lyestufl's of claim-7.

30o la-Material, dyed-with the, dyestues "of v t claim'll.

QcIaim-S." V -4 v a o .7 15.'Materialdyed with" thedyestufi'sof claim 9.

I Material dy d tht'the. dyestuffs of v f 35c1aimvl0. a a

17. Material dyed the dyestufis of g 18. Material dyed; with d yestufisof c1aim'12l V /"In witness whereof we hjave hereunto signeclour namesthis 5th 'day'of July,1928.

qosoAR BALLY. V a v AUL ll A N- 1 t' a.

